X-ray study on the phase transitions in triammonium hydrogen disulfate crystals and deuterated crystals

The structural phase transitions in triammonium hydrogen disulfate crystals and deuterated crystals below room temperature have been studied by X-ray diffraction. Three phases are observed in the temperature range from 25°C down to — 160°C. The space groups in three different phases are identified as C2/c, P2/n (or Pn), and C2 for (NH₄)₃H(SO₄)₂ and (ND₄)₃D(SO₄)₂ crystals. No isotope effect on the structural phase transitions in these crystals could be detected by these studies. The occurrence of structural phase transitions caused by the reorientation of SO₄ groups and/or the shift of oxygen atoms from the sulfate atom in the SO₄ group are suggested from the diffraction photographs.     

Structural studies of the P-T phase diagram of sodium niobate

The crystal structure of sodium niobate (NaNbO₃) has been investigated by energy-dispersive X-ray diffraction at high pressures (up to 4.3 GPa) in the temperature range 300–1050 K. At normal conditions, NaNbO₃ has an orthorhombic structure with Pbcm symmetry (antiferroelectric P phase). Upon heating, sodium niobate undergoes a series of consecutive transitions between structural modulated phases P-R-S-T(1)-T(2)-U; these transitions manifest themselves as anomalies in the temperature dependences of the positions and widths of diffraction peaks. Application of high pressure leads to a decrease in the temperatures of the structural transitions to the R, S, T(1), T(2), and U phases with different baric coefficients. A phase diagram for sodium niobate has been build in the pressure range 0–4.3 GPa and the temperature range 300–1050 K. The dependences of the unit-cell parameters and volume on pressure and temperature have been obtained. The bulk modulus and the volume coefficients of thermal expansion have been calculated for different structural modulated phases of sodium niobate. A phase transition (presumably, from the antiferroelectric orthorhombic P phase to the ferroelectric rhombohedral N phase) has been observed at high pressure (P = 1.6 GPa) and room temperature.     

Low-temperature phase transitions in LiKSO4: A neutron study

A single crystal neutron diffraction study of the low temperature structural phase transitions in LiKSO₄ has been carried out. Detailed temperature dependence of the Bragg peak profiles and integrated intensities for a group of about 20 reflections has been investigated upon cooling and heating in the temperature range 300 K to 96 K. The crystal undergoes three clear phase transitions at 205 K (from sp. gr. P6₃ to sp. gr. P31c), at 189 K and at about 135 K on cooling. The corresponding temperatures are 250 K, 190 K and 138 K on the heating cycle. These transitions are extremely sluggish, the kinetics depending on the thermal treatment of the crystal.     

Phase transitions in 3,5-dichloropyridine

Abstract

Structural phase transitions in 3,5-dichloropyridine crystal have been studied by calorimetry (150–300 K), X-ray diffraction (300 K), ³⁵Cland ¹⁴N nuclear quadrupole resonance (75–300 K) and vibrational spectroscopy (20–300K). Three phases have been shown to exist: phase I, between 338 and 287.5 K, phase 11, between 287.5 and 167.5 K, and phase 111, below 167.5 K. Phase I is characterised by the space group P 2,/m and Z = 2 whereas phases I1 and 111 remain centrosymmetric but double the unit cell. All the phases are ordered and contain crystallo- graphically equivalent molecules. The I ? I1 transition is of first order and probably of the reconstructive type while the II ? III transition is believed to be displacive. Both transitions are monitored by predominantly R′_x and R′_z librational motions.     

Structural and magnetic phase transitions in mixed-valence cobalt oxides REBaCo4O7 (RE=Lu,Yb, Tm)

New mixed valence Co oxides REBaCo₄O₇ (RE=Lu, Yb, Tm) show structural first-order phase transitions from hexagonal (P6₃mc) to orthorhombic (Cmc2₁ or lower) system below 170, 180, and 230 K, respectively. The low-temperature phases order magnetically at 47, 75, and 105 K, respectively.     

Properties of a new ferroelectric crystal family: MCd(NO2)3 [M=NH4, K,Rb, Cs,Tl]

Single crystals of MCd(NO₂)₃, with M=NH₄, K, Rb, Cs, and Tl, respectively, were grown and investigated by means of optical and dielectric methods. The crystals show rhombohedral symmetry (possible space group R 3) and multi-domain patterns at ambient temperature. The compounds exhibit phase transitions above room-temperature of first (M=K) and second order (M=Rb, Cs, Tl), respectively, into cubic high-temperature phases. Observed dielectric anomalies and hysteresis loops point to ferroelectric properties and suggest a relaxational order-disorder mechanism of the nitrite ions to be responsible for the transitions. The MCd-(NO₂)₃-compounds are seen to represent a new family of ferroelectrics with a cubic prototypic phase closely related to the structural type of the perovskites. The transions are classified by symmetry considerations, and a possible structure of the cubic high-temperature phase with space group Pm3 is proposed.     

X-ray study of structural phase transitions in nanocrystalline LaMnO3+δ perovskite

The nanocrystalline LaMnO_3+δ perovskite was synthesized by the microwave-assisted glycothermal method and calcined at several temperatures up to 1500°C. The prepared samples were examined by the X-ray powder diffraction with the aim to show that LaMnO_3+δ exhibits the size-induced structural phase transitions. The as-received nanocrystals of LaMnO_3+δ are of tetragonal, pseudo-cubic symmetry not known for bulk material. The samples calcined at temperatures 750–1100°C have trigonal symmetry known from the high-temperature phase of LaMnO₃ single crystal. The samples calcined from 1200°C to 1500°C have two phases: trigonal and orthorhombic. Thus, the observed phase sequence is inverted with respect to that of the bulk material, which is the characteristic of the size-induced mechanism of phase transitions in the nanocrystals. The critical crystallite sizes for both structural transitions were evaluated as 20 and 100?nm.     

Theoretical predictions of the structural,mechanical and lattice dynamical properties of XW2 (X = Zr,Hf) Laves phases

We have investigated the structural, mechanical and lattice dynamical properties of ZrW₂ and HfW₂ compounds in cubic C15 (space group Fd-3m), hexagonal C14 (space group P6₃/mmc) and C36 (space group P6₃/mmc) phases using generalized gradient approximation within the plane-wave pseudo-potential density functional theory. We have found that ZrW₂ and HfW₂ in cubic C15 phase are the most stable among the considered phases. From calculated elastic constants, it is shown that all phases are mechanically stable according to the elastic stability criteria. The related mechanical properties, such as bulk, shear and Young moduli, Poisson’s ratio, Debye temperature and hardness have been also calculated. The results show that ZrW₂ and HfW₂ compounds are ductile in nature with respect to the B/G and Cauchy pressure analysis. The phonon dispersion curves, phonon density of states and some thermodynamic properties are computed and discussed exhaustively for considered phases.     

Temperature evolution of the infrared spectrum of Ni(ClO4)2·6H2O

Temperature evolution of the infrared spectrum of the title compound confirms the phase transition temperatures 223, 311 and 355 K reported earlier and suggests a new phase transition at 180 K. From the spectral evidence, the transitions below the room temperature (～300 K) are attributed to tumbling motion of the metal aquo-complex, while those above the room temperature are attributed to reorientational motion of the water molecule. The space group in low temperature phases is suggested to be C²_s.     

Electronic absorption spectrum of Cs<Subscript>2</Subscript>ZnI<Subscript>4</Subscript> thin films

The absorption spectrum of Cs₂ZnI₄ thin films in the energy range 3–6 eV at temperatures from 90 to 340 K has been investigated. It is established that this compound belongs to direct-gap insulators. Low-frequency exciton excitations are localized in ZnI₄ structural elements of the lattice. Phase transitions at 280 K (paraelectric phase ? incommensurate phase), 135 K (incommensurate phase ? monoclinic ferroelastic phase), and 96 K (monoclinic phase ? triclinic ferroelastic phase) have been found from the temperature dependences of the spectral position and halfwidth of the low-frequency exciton band. Additional broadening of the exciton band is observed for ferroelastic phases; it is likely to be due to exciton scattering from strain fluctuations near domain walls.     

Effect of phase transformation on optical and dielectric properties of zirconium oxide nanoparticles

Zirconium oxide nanoparticle (ZrO₂) is synthesized by the hydrothermal method at different calcination temperatures. The structural analysis is carried out by X-ray diffraction and Raman spectra. The sample prepared at 400 °C and 1100 °C showed the cubic and monoclinic phase, respectively, and the sample calcined at 600 °C and 800 °C showed the mixed phase with co-existence of cubic and monoclinic phases. Furthermore, the morphology and particle size of these samples were investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis. The band gap estimated from UV–Vis spectra of ZrO₂ (zirconia) nanocrystalline materials calcined at different temperatures from 400 °C to 1100 °C was in the range of 2.6–4.2 eV. The frequency dependence of dielectric constant and dielectric loss was investigated at room temperature. The low frequency region of dielectric constant is attributed to space charge effects.     

Influence of crystallization treatment on structure,magnetic properties and magnetocaloric effect of Gd71Ni29 melt-spun ribbons

The influence of crystallization treatment on the structure, magnetic properties and magnetocaloric effect of Gd₇₁Ni₂₉ melt-spun ribbons has been investigated in detail. Annealing of the melt-spun samples at 610 K for 30 min, a majority phase with a Fe₃C-type orthorhombic structure (space group, Pnma) and a minority phase with a CrB-type orthorhombic structure (space group, Cmcm) were obtained in the amorphous matrix. The amorphous melt-spun ribbons undergo a second-order ferromagnetic to paramagnetic phase transition at 122 K. For the annealed samples, two magnetic phase transitions caused by amorphous matrix and Gd₃Ni phases occur at 82 and 100 K, respectively. The maximum magnetic entropy change (–ΔS_M)^max is 9.0 J/(kgˑK) (5T) at 122 K for the melt-spun ribbons. The values of (–ΔS_M)^max in annealed ribbons are 1.0 and 5.7 J/(kgˑK), corresponding to the two adjacent magnetic transitions.     

Incommensurate cooperative tilting modes of MnF6 octahedra relatedto the structural phasetransitions in BaMnF4

The structural phase transitions of the layer compound BaMnF₄ were studied by high-resolution X-ray diffraction using synchrotron radiation. The intensities and profiles of two kinds of superlattice reflections having incommensurate reduced wave vectors q ₁= (～ ± 1/5,0,0) _p and q ₂ =(～ ± 2/5,1/2,1/2)_p, respectively, were measured as a function of temperature from 25 K to 280 K. These temperature dependencies show that incommensurate structural phase transitions of second order occur at 234 K and 244 K. These structural phase transitions are interpreted as successive condensations of a folding-screen-like incommensurate plane-distortion mode and a commensurate anti-ferro-distortive tilting mode of the MnF₆ octahedra around the primitive a₀ - and b₀ -axes, when cooled down. It is also found that there is another structural phase transition at about 45 K related to a precursor structural distortion for the antiferromagnetic transition occurring at about 26 K.     

Editorial

This review contains up-to-date information about experimental and theoretical investigations of phase transitions and specific features of properties of mixed crystals involving the incipient ferroelectric KTaO₃ with the off-center Li⁺, Nb⁵⁺, Na⁺ impurities. Main attention is paid to the results of the study of the mixed systems by radiospectroscopy methods (ESR and NMR).

Theoretical criteria and experimental evidence of ferroelectric and ferroelastic phase transitions as well as of dipole and quadrupolar glass states induced by the off-center impurities are discussed. It is shown that at high enough concentrations of the off-center impurities phases with long-range order appear, but at low concentrations dipole glass states occur. At intermediate concentrations of the off-center impurities new phases appear in which the coexistence of long-range properties and those of dipole glasses is possible. These phases could be named ferroelectric or ferroelastic glasses to stress their similarity with the ferroglass phases which were discovered earlier in mixed magnetic systems. The usefulness of radiospectroscopy methods for the study of phase transitions induced by off-center impurities in mixed systems, which can be considered as model disordered systems, is underlined.

In conclusion, some questions on the physics of phase transitions in disordered systems which should be solved in the future are discussed.     

Birefringence,X-ray and neutron diffraction measurements on the structural phase transitions of (CH3NH3)2 MnCl4 and (CH3NH3)2FeCl4

We used optical birefringence, X-ray and neutron diffraction methods with single crystals to study the structural phase transitions of the perowskite-type layer structures of (CH₃NH₃)₂MeCl₄ with Me=Mn, Fe. The Mn-compound shows the following structural transitions at 394 K — a continuous order-disorder phase transition from tetragonal symmetry $\text{I4}\text{mmm}$ to orthorhombic space group Abma (Cmca in reference 10); at 257 K — a discontinuous transition to a second tetragonal modification; at 95 K — a discontinuous transition to a monoclinic phase. For the Fe-compound the corresponding transition temperatures are 328 K and 231 K, respectively. A low temperature monoclinic phase could not be observed. The lattice parameters of the different modifications were determined as a function of temperature. The temperature dependent course of the order parameter has been investigated for the order—disorder transition. For both compounds, all the methods used gave the same value for the critical exponent of β = 0.315.     

The influence of oxidation temperature on structural, optical and electrical properties of thermally oxidized bismuth oxide films

Monoclinic bismuth oxide (Bi₂O₃) films have been prepared by thermal oxidation of vacuum evaporated bismuth thin films onto the glass substrates. In order to obtain the single phase Bi₂O₃, the oxidation temperature was varied in the range of 423-573 K by an interval of 50 K. The as-deposited bismuth and oxidized Bi₂O₃ films were characterized for their structural, surface morphological, optical and electrical properties by means of X-ray diffraction, scanning electron microscopy (SEM), optical absorption and electrical resistivity measurements, respectively. The X-ray analyses revealed the formation of polycrystalline mixed phases of Bi₂O₃ (monoclinic, α-Bi₂O₃ and tetragonal, β-Bi₂O₃) at oxidation temperatures up to 523 K, while at an oxidation temperature of 573 K, a single-phase monoclinic α-Bi₂O₃ was formed. From SEM images, it was observed that of as-deposited Bi films consisted of the well-defined isolated crystals of different shapes while after thermal oxidation the smaller dispersed grains were found to be merged to form bigger grains. The changes in the optical properties of Bi₂O₃ films obtained by thermal oxidation at various temperatures were studied from optical absorption spectra. The electrical resistivity measurement depicted semiconducting nature of Bi₂O₃ with high electrical resistivity at room temperature.     

Temperature-pressure phase diagram of CsHSO4

Abstract

On the basis of group theoretical analysis of phase transitions between the phases with known space symmetries the space symmetries of high pressure phases are theoretically predicted. A part of temperaturepressure phase diagram of CsHSO₄ in the region of high temperatures and pressures is theoretically constructed. It is shown that the new pahse of the C¹ _2h space symmetry can be observed at high pressures.     

Piezoelectric resonance study of structural phase transitions in BaMnF4

Structural transitions of BaMnF₄ are studied by piezoelectric resonance. The results show that large structural modulations occur from 220 K to 250 K. It is found from the temperature-dependence of the resonance curves that successive phase transitions appear at about 226 K, 234 K and 244 K. The inconsistency of the transition temperature from a A2₁ am to an incommensurate phase is interpreted as intrinsic structural instability, but not by defects or impurities in the crystal of BaMnF₄ used.     

Spin dynamics and structural phase transitions in quasi-2D antiferromagnets R2CuO4 (R=Pr, Sm, and Eu)

Spin and lattice dynamics of R₂CuO₄ (R=Pr, Sm, and Eu) crystals were studied over the frequency and temperature ranges 20–250 GHz and 5–350 K, respectively. The absorption coefficients of the R₂CuO₄ crystals (R=Pr, Sm, and Eu) were found to change dramatically at temperatures of, respectively, 20, 80, and 150 K over a broad frequency range above 120 GHz. The absorption jumps were caused by the structural phase transitions. Broad spin-wave bands were observed in the high-temperature phases of all crystals studied. Absorption lines due to lattice dynamics were observed near the temperatures of structural phase transition over a broad frequency range, including the frequencies corresponding to the spin-wave bands.     

The effect of a magnetic field on Jahn-Teller ordering in the monoclinic crystal RbDy(WO4)2

This paper presents the results of a study of the thermal properties of monoclinic single-crystal RbDy(WO₄)₂ at temperatures of 2–15 K and in magnetic fields up to 6 T. From the results of measurements of the heat capacity and thermograms, two structural phase transitions are detected, at T _c1=4.9 K and T _c2=9.0 K. The transformation from the high-temperature phase to the low-temperature phase occurs via an intermediate phase. The field dependences of the critical temperatures are found for various magnetic-field orientations. H-T phase diagrams are constructed for H‖a and H‖c. An anomalous increase (by almost an order of magnitude) of the relaxation time of the system, associated with structural instability of the crystal lattice, is detected in the region of the structural phase transitions. A symmetry analysis is carried out, and possible crystal structures of the low-temperature phase are indicated. Fiz. Tverd. Tela (St. Petersburg) 40, 2221–2225 (December 1998)